Unified Synthesis of Azepines by Visible-Light-Mediated Dearomative Ring Expansion of Aromatic <i>N</i>-Ylides

Abstract

Herein, we report a unified approach to azepines by dearomative photochemical rearrangement of aromatic N-ylides. Deprotonation of quaternary aromatic salts with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or N,N,N′,N’-tetramethylquanidine (TMG) under visible light irradiation provides mono- and polycyclic azepines in yields up to 98%. This ring-expansion presents a new mode of access to functionalized azepines from N-heteroarenes using two straightforward steps and simple starting materials.

Topics & Concepts